CN114207017B - curable composition - Google Patents

Abstract

The present invention provides a multi-component curable composition, which comprises A agent and B agent, and the A agent comprises a polyoxyalkylene polymer having a reactive silicon group represented by the general formula (1) (A ), a (meth)acrylate polymer (B) having a reactive silicon group represented by general formula (1), an epoxy resin curing agent (D) having a tertiary amine, and an amine having an alicyclic structure (E1), the B agent contains epoxy resin (C). In addition, the multi-component curable composition contains A agent and B agent, and the A agent includes the above-mentioned polymer (A), the above-mentioned polymer (B), and an epoxy resin curing agent (D) having a tertiary amine. , the B agent contains an epoxy resin (C), and either or both of the A agent and the B agent contain an aminoalcohol compound (E2). -SiR ⁵ _c X _3-c (1) (wherein, R ⁵ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1).

Description

curable composition

technical field

The present invention relates to a multi-component curable composition.

Background technique

In vehicles, airplanes, and railways, in order to reduce the weight, as a structural member, the replacement of aluminum, magnesium, and carbon fiber composite materials other than steel is progressing, and the multi-materialization of using multiple materials in one body is progressing. Increase. Since spot welding and laser welding may be difficult in joining dissimilar materials, attention has been paid to adhesive joining using an adhesive. Since steel plates, aluminum alloys, and fiber-reinforced composite materials have different coefficients of linear expansion, flexibility to follow thermal deformation is required for this adhesive. Therefore, high-rigidity epoxy resins are sometimes disadvantageous, and therefore, materials with a high modulus of elasticity and flexibility are required as new structural adhesives.

As an adhesive, a composition formed of a reactive silicon group-containing polyoxyalkylene polymer and an epoxy resin having both high breaking strength and flexibility is known (for example, refer to Patent Document 1), but as a structural member Adhesives sometimes have insufficient strength.

Regarding this point, Patent Document 2 discloses that the following multi-component curable composition can form a cured product exhibiting high strength, high rigidity, and flexibility, and can be used as a structural adhesive. The typed curable composition comprises an agent A and an agent B containing an epoxy resin, the agent A comprising a polyoxyalkylene-based polymer having more than one reactive silicon group at one end, a reactive silicon group-containing (meth)acrylate polymers.

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 02-214759

Patent Document 2: International Publication No. 2019/069866

Contents of the invention

The problem to be solved by the invention

Usually, after the adherend is joined by an adhesive formed of an organic polymer having a reactive silicon group and an epoxy resin, a long-term curing (curing) process of several days is performed to exhibit given physical properties .

However, structural adhesives are sometimes used to join adherends in a continuous production line. In such a case, after bonding the adherends, a heating step is performed for a short time, and the structural adhesive is semi-hardened, and then the process proceeds to the next step. At this time, in order to ensure operability in the next step and onwards, the semi-cured structural adhesive is required to exhibit a certain degree of rigidity.

According to the structural adhesive described in Patent Document 2, although a high-strength cured product can be obtained after a long curing process, there is a problem that the rigidity exhibited by a relatively short heating process does not reach a sufficient level. The problem of slow increase in rigidity.

In view of the above-mentioned circumstances, an object of the present invention is to provide a curable composition capable of expressing high rigidity through a short heating process, and a cured product obtained by curing the composition.

Solution to the problem

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, found that by using reactive silicon group-containing polyoxyalkylene polymers, reactive silicon group-containing (meth)acrylate polymers, and The present invention has been accomplished by incorporating an amine having an alicyclic structure or an aminoalcohol compound in a multi-component curable composition containing an epoxy resin to solve the above-mentioned problems.

That is, the first aspect of the present invention relates to a multi-component curable composition comprising an A agent and a B agent. Vinyl polymer (A), (meth)acrylate polymer (B) having a reactive silicon group represented by the general formula (1), a ring having a tertiary amine other than an amine having an alicyclic structure An epoxy resin curing agent (D), and an amine (E1) having an alicyclic structure, the B agent includes an epoxy resin (C).

-SiR ⁵ _c X _3-c (1)

(In the formula, ^R5 is a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1.)

The amine (E1) preferably having an alicyclic structure is a compound in which an amino group is directly bonded to an alicyclic skeleton.

In addition, a second aspect of the present invention relates to a multi-component curable composition comprising an agent A and an agent B, the agent A comprising a polyoxygen compound having a reactive silicon group represented by the general formula (1). Vinyl polymer (A), (meth)acrylate polymer (B) having a reactive silicon group represented by general formula (1), and epoxy resin curing with tertiary amines other than aminoalcohol compounds agent (D), the agent B contains an epoxy resin (C), and either or both of the agents A and B contain an aminoalcohol compound (E2).

-SiR ⁵ _c X _3-c (1)

(In the formula, ^R5 is a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1.)

The aminoalcohol compound (E2) is preferably an aminoalcohol compound not having an aromatic ring. Preferably, the aminoalcohol compound (E2) is a triolamine.

In the above two forms, it is preferable that the reactive silicon group of the polyoxyalkylene polymer (A) is a trimethoxysilyl group. Preferably, the reactive silicon group of the (meth)acrylate polymer (B) is a trimethoxysilyl group. The terminal portion of the polyoxyalkylene polymer (A) is preferably represented by the general formula (2).

[chemical formula 1]

In the formula, R ¹ and R ³ are each independently a divalent bonding group with 1 to 6 carbon atoms, and atoms bonded to each carbon atom adjacent to R ¹ and R ³ are carbon, oxygen, nitrogen any atom in . R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1-10. R ⁵ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X is a hydroxyl group or a hydrolyzable group. c means 0 or 1. Preferably R ¹ is CH ₂ OCH ₂ and R ³ is CH ₂ . Preferably, R ² and R ⁴ are each a hydrogen atom. Preferably (meth)acrylic acid ester polymer (B) is the polymer that uses monomer (b1) and macromonomer (b2) as constituent monomer, and described monomer (b1) has reactive silicon group and polymerization a permanent unsaturated group, and the macromonomer (b2) is a (meth)acrylate polymer having a polymerizable unsaturated group.

In addition, the present invention is a structural adhesive composed of the above-mentioned multi-component curable composition, and also a cured product obtained by curing the above-mentioned multi-component curable composition.

The effect of the invention

According to the present invention, it is possible to provide a curable composition capable of exhibiting high rigidity through a short heating process, and a cured product obtained by curing the composition.

Detailed ways

Hereinafter, although embodiment of this invention is demonstrated concretely, this invention is not limited to these embodiment.

The first aspect of the present invention is a multi-component curable composition comprising an agent A and an agent B, the agent A containing a polyoxyalkylene having a reactive silicon group represented by the following general formula (1) Polymer (A), a (meth)acrylate polymer (B) having a reactive silicon group represented by the following general formula (1), a ring having a tertiary amine other than an amine having an alicyclic structure An epoxy resin curing agent (D), and an amine (E1) having an alicyclic structure, the B agent includes an epoxy resin (C).

The second aspect of the present invention is a multi-component curable composition comprising an A agent and a B agent, and the A agent contains a polyoxyalkylene having a reactive silicon group represented by the following general formula (1) Polymer (A), (meth)acrylate polymer (B) having a reactive silicon group represented by the following general formula (1), and epoxy resin curing with tertiary amines other than aminoalcohol compounds agent (D), the agent B contains an epoxy resin (C), and either or both of the agents A and B contain an aminoalcohol compound (E2).

＜＜Polyoxyalkylene polymer (A) with reactive silicon group＞＞

＜Reactive silicon base＞

The polyoxyalkylene polymer (A) has a reactive silicon group represented by the general formula (1).

-SiR ⁵ _c X _3-c (1)

(In the formula, ^R5 is a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1.)

The number of carbon atoms in the hydrocarbon group of R ⁵ is preferably 1-10, more preferably 1-5, even more preferably 1-3. Specific examples of ^R5 include, for example, methyl, ethyl, chloromethyl, methoxymethyl, and N,N-diethylaminomethyl. Methyl, ethyl, chloromethyl, and methoxymethyl are preferred, and methyl and methoxymethyl are more preferred.

Examples of X include hydroxyl group, halogen, alkoxy group, acyloxy group, ketoxime group, amino group, amido group, acid amido group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, alkoxy groups such as methoxy and ethoxy are more preferable from the viewpoint of mild hydrolyzability and ease of handling, and methoxy and ethoxy are particularly preferable.

Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a tris(2-propyleneoxy)silyl group, Acetoxysilyl, Dimethoxymethylsilyl, Diethoxymethylsilyl, Dimethoxyethylsilyl, (Chloromethyl)dimethoxysilyl, (Chloromethyl)diethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N-diethyl (N,N-diethylaminomethyl)diethoxysilyl and the like, but are not limited thereto. Among them, methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxy Dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group show high activity, can get good mechanical Since the cured product has physical properties, it is preferable, and from the viewpoint of obtaining a highly rigid cured product, it is more preferably a trimethoxysilyl group or a triethoxysilyl group, and even more preferably a trimethoxysilyl group.

The polyoxyalkylene polymer (A) may have an average of more than one reactive silicon group at one terminal site. Having an average of more than one reactive silicon group at one terminal site means that polyoxyalkylene-based polymers (A) include those represented by the following general formula (2) having two reactive silicon groups at one terminal site The above reactive silicon-based polyoxyalkylenes. That is, the polyoxyalkylene-based polymer (A) may contain only polyoxyalkylenes having two or more reactive silicon groups at one terminal, or may contain polyoxyalkylenes having two or more reactive silicon groups at one terminal. Both an alkylene oxide and a polyoxyalkylene having one reactive silicon group at one terminal site. In addition, the plurality of terminal sites included in one molecule of polyoxyalkylene may be both a terminal site having two or more reactive silicon groups and a terminal site having one reactive silicon group. In addition, the polyoxyalkylene-based polymer (A) has an average of more than one reactive silicon group at one terminal site in total, but may contain a polyoxyalkylene-based terminal site that does not have a reactive silicon group.

[chemical formula 2]

(In the formula, R ¹ and R ³ are each independently a divalent bonding group with 1 to 6 carbon atoms, and the atoms bonded to each carbon atom adjacent to R ¹ and R ³ are carbon, oxygen, Any atom in nitrogen. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group with 1 to 10 carbon atoms. n is an integer of 1 to 10. R ⁵ , X, and c are as described above in formula (1) .)

R ¹ and R ³ may be a divalent organic group having 1 to 6 carbon atoms, or a hydrocarbon group including an oxygen atom. The number of carbon atoms in the hydrocarbon group is preferably 1-4, more preferably 1-3, even more preferably 1-2. Specific examples of R ¹ include, for example, CH ₂ OCH ₂ , CH ₂ O, and CH ₂ , preferably CH ₂ OCH ₂ . Specific examples of R ³ include, for example, CH ₂ and CH ₂ CH ₂ , preferably CH ₂ .

The number of carbon atoms in the hydrocarbon group of R ² and R ⁴ is preferably 1-5, more preferably 1-3, even more preferably 1-2. Specific examples of R ² and R ⁴ include, for example, a hydrogen atom, a methyl group, and an ethyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

According to a particularly preferred embodiment, R ¹ at the end represented by the general formula (2) is CH ₂ OCH ₂ , R ³ is CH ₂ , and R ² and R ⁴ are hydrogen atoms. n is preferably an integer of 1-5, more preferably an integer of 1-3, still more preferably 1 or 2. Among them, n is not limited to one value, and multiple values may exist mixedly.

The polyoxyalkylene polymer (A) preferably has an average of more than 1.0 reactive silicon groups at one terminal site, more preferably 1.1 or more, further preferably 1.5 or more, still more preferably 2.0 or more. In addition, it is preferably 5 or less, and more preferably 3 or less.

The number of terminal sites having more than one reactive silicon group contained in one molecule of the polyoxyalkylene polymer (A) is preferably 0.5 or more on average, more preferably 1.0 or more, still more preferably 1.1 or more, and still more preferably 1.1 or more. More preferably, it is 1.5 or more. In addition, it is preferably 4 or less, and more preferably 3 or less.

The polyoxyalkylene-based polymer (A) may have a reactive silicon group other than the terminal part, but it has a reactive silicon group only at the terminal part, and it is easy to obtain a rubber-like cured product with high elongation and low elastic modulus, Therefore preferred.

The average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.2 or more, still more preferably 1.3 or more, still more preferably 1.5 or more, particularly preferably 1.7 or more. In addition, it is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less. When the average number of reactive silicon groups per molecule is 1.0 or less, there is a possibility that a high-strength cured product cannot be obtained. When the average number of reactive silicon groups per molecule exceeds 6.0, there is a possibility that a cured product with high elongation cannot be obtained.

＜Main chain structure＞

The main chain skeleton of the polyoxyalkylene polymer (A) is not particularly limited, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene Oxypropylene-polyoxybutylene copolymer, etc. Among them, polyoxypropylene is preferable.

The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, particularly preferably 3,000 to 30,000, in terms of polystyrene equivalent molecular weight in GPC. When the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced increases, which may cause disadvantages in terms of production costs. When it exceeds 100,000, the viscosity tends to be high, which tends to be disadvantageous in terms of workability.

As the molecular weight of the polyoxyalkylene-based polymer (A), the organic polymer precursor before the reactive silicon group is introduced, according to the method for measuring the hydroxyl value in accordance with JIS K 1557 and the method for measuring the iodine value specified in JIS K 0070 According to the titration analysis based on the principle, the terminal group concentration can be directly measured, and it can also be expressed by the terminal group conversion molecular weight obtained in consideration of the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). The terminal group-equivalent molecular weight of the polyoxyalkylene-based polymer (A) can also be obtained by making a calibration between the number-average molecular weight of the organic polymer precursor obtained by ordinary GPC measurement and the above-mentioned terminal group-equivalent molecular weight. In the graph, the number-average molecular weight of the polyoxyalkylene-based polymer (A) obtained by GPC was converted into an end group-equivalent molecular weight.

The molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, specifically preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less. In addition, it is preferably 1.2 or less from the viewpoint of improving the durability and elongation of the cured product and improving various mechanical properties. The molecular weight distribution of the polyoxyalkylene-based polymer (A) can be determined from the number average molecular weight and weight average molecular weight measured by GPC.

In addition, the main chain structure of the polyoxyalkylene polymer (A) may be linear or branched.

＜Synthesis method of polyoxyalkylene polymer (A)＞

Next, the synthesis method of the polyoxyalkylene polymer (A) is demonstrated.

A polyoxyalkylene-based polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal of a preferred embodiment is preferably obtained by forming a polyoxyalkylene-based polymer (A) at one terminal of a hydroxyl-terminated polymer obtained by polymerization After introducing two or more carbon-carbon unsaturated bonds, react with a reactive silicon group-containing compound that reacts with carbon-carbon unsaturated bonds. Hereinafter, the above-mentioned preferred synthesis method will be described.

(polymerization)

For the polyoxyalkylene-based polymer (A), it is preferable to use a composite metal cyanide complex catalyst such as zinc hexacyanocobaltate ethylene glycol dimethyl ether complex to combine an epoxy compound with a hydroxyl group. Initiator polymerization method.

Examples of the initiator having a hydroxyl group include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxyglycerol, allyl alcohol, polyoxypropylene monoallyl ether, polyoxypropylene mono Compounds having one or more hydroxyl groups, such as alkyl ethers.

Examples of the epoxy compound include alkylene oxides such as ethylene oxide and propylene oxide, glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether, and the like. Among them, propylene oxide is preferable.

(Introduction of carbon-carbon unsaturated bond)

As a method of introducing two or more carbon-carbon unsaturated bonds at one terminal, it is preferable to use a method of reacting an alkali metal salt with a hydroxyl-terminated polymer, and then first reacting with an epoxy compound having a carbon-carbon unsaturated bond, This is followed by reaction with a halogenated hydrocarbon compound having carbon-carbon unsaturation. By using this method, the molecular weight and molecular weight distribution of the polymer main chain can be controlled according to polymerization conditions, and reactive groups can be introduced more efficiently and stably.

As the alkali metal salt, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, and potassium ethoxide are preferred, and sodium methoxide and potassium methoxide are more preferred. From the viewpoint of availability, sodium methoxide is particularly preferable.

The temperature at the time of reacting the alkali metal salt is preferably 50°C to 150°C, more preferably 110°C to 140°C. The time for reacting the alkali metal salt is preferably not less than 10 minutes and not more than 5 hours, more preferably not less than 30 minutes and not more than 3 hours.

As the epoxy compound having a carbon-carbon unsaturated bond, a compound represented by the general formula (3) is particularly suitably used.

[chemical formula 3]

R ¹ and R ² in the formula are the same as above. Specifically, from the viewpoint of reactivity, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, epoxybutylene, 1,4- Cyclopentadiene monoepoxide, allyl glycidyl ether is particularly preferred.

The amount of the epoxy compound having a carbon-carbon unsaturated bond can be added in consideration of the introduction amount and reactivity of the carbon-carbon unsaturated bond to the polymer, and any amount can be used. In particular, the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.2 or more, more preferably 0.5 or more. In addition, it is preferably 5.0 or less, and more preferably 2.0 or less.

The reaction temperature for the ring-opening addition reaction between the epoxy compound having a carbon-carbon unsaturated bond and the hydroxyl group-containing polymer is preferably 60°C to 150°C, more preferably 110°C to 140°C.

Examples of halogenated hydrocarbon compounds having a carbon-carbon unsaturated bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, iodoethylene, Allyl iodide, methallyl iodide, and the like are more preferably used from the viewpoint of ease of handling, such as allyl chloride and methallyl chloride.

The addition amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is not particularly limited, but the molar ratio to the hydroxyl groups of the hydroxyl-terminated polymer is preferably 0.7 or more, more preferably 1.0 or more. In addition, it is preferably 5.0 or less, and more preferably 2.0 or less.

The temperature at which the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted is preferably 50°C to 150°C, more preferably 110°C to 140°C. The reaction time is preferably not less than 10 minutes and not more than 5 hours, more preferably not less than 30 minutes and not more than 3 hours.

(Introduction of reactive silicon groups)

The method for introducing a reactive silicon group is not particularly limited, and known methods can be used. The following example shows the import method.

(i) A method of adding a hydrosilane compound to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction.

(ii) A polymer having a carbon-carbon unsaturated bond and a compound having both a group capable of reacting with a carbon-carbon unsaturated bond to form a bond and a reactive silicon group (also called a silane coupling agent) The method of performing the reaction. Examples of groups capable of reacting with carbon-carbon unsaturated bonds to form bonds include mercapto groups and the like, but are not limited thereto.

(iii) A method of reacting a reactive group-containing polymer with a silane coupling agent. Examples of combinations of reactive group-containing polymers and reactive groups of silane coupling agents include: hydroxyl and isocyanate groups, hydroxyl and epoxy groups, amino and isocyanate groups, amino and thioisocyanate groups, amino and Epoxy group, amino group and α,β-unsaturated carbonyl group (reaction based on Michael addition), carboxyl group and epoxy group, unsaturated bond and mercapto group, etc., but not limited thereto.

The method (i) is preferable because the reaction is simple, the adjustment of the introduced amount of the reactive silicon group, and the physical properties of the obtained reactive silicon group-containing polyoxyalkylene polymer (A) are stable. The methods (ii) and (iii) are preferable since there are many reaction options and the introduction rate of the reactive silicon group is easy to increase.

The hydrosilane compound usable in the method (i) is not particularly limited, and examples include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, diacetoxysilane, Methoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl base) dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl ) diethoxysilane, etc.

As the amount of the hydrosilane compound used, from the viewpoint of reactivity, the molar ratio (number of moles of hydrosilane/number of moles of carbon-carbon unsaturated bonds) to the carbon-carbon unsaturated bond in the polymer as a precursor Preferably it is 0.05-10, More preferably, it is 0.3-2 from an economical viewpoint.

The hydrosilylation reaction can be accelerated using various catalysts. As the hydrosilylation catalyst, known catalysts such as various complexes of cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium and the like can be used. For example, catalysts in which platinum is supported on supports such as alumina, silica, and carbon black; chloroplatinic acid; chloroplatinic acid complexes formed from chloroplatinic acid and alcohols, aldehydes, and ketones; platinum- Olefin complexes [eg Pt(CH ₂ ═CH ₂ ) ₂ (PPh ₃ ), Pt(CH ₂ ═CH ₂ ) ₂ Cl ₂ ]; platinum-vinylsiloxane complexes [Pt{(vinyl)Me ₂ SiOSiMe ₂ (vinyl)}, Pt{Me(vinyl)SiO} ₄ ]; platinum-phosphine complexes [Ph(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ]; platinum-phosphite complexes [ Pt{P(OPh) ₃ } ₄ ] and so on. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinylsiloxane complex are preferably used.

Examples of silane coupling agents that can be used in the method (ii) or (iii) above include 3-mercaptopropyltrimethoxysilane that reacts with unsaturated bonds, 3-mercaptopropyldimethoxymethylsilane, mercaptosilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyldimethoxymethylsilane and other mercaptosilanes; 3-isocyanatopropyltrimethoxy 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanate Isocyanate-based silanes such as methyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxy that react with hydroxyl, amino or carboxyl groups Methylsilane, 3-Glycidoxypropyltriethoxysilane, Glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, Glycidoxymethylsilane Epoxy silanes such as dimethoxymethylsilane; 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3- Aminopropyltriethoxysilane, 3-(2-aminoethyl)propyltrimethoxysilane, 3-(2-aminoethyl)propyldimethoxymethylsilane, 3-(2-amino Ethyl)propyltriethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, 3-ureapropyltrimethoxysilane, 3-ureapropyltriethoxy ylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexyl Aminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxy Amino silanes such as dimethylsilyl)propyl]ethylenediamine, bis(3-(trimethoxysilyl)propyl)amine; 3-hydroxypropyltrimethoxysilane, hydroxymethyltriethoxy Hydroxyalkylsilanes such as silane, etc.

The main chain of the polyoxyalkylene polymer (A) may contain an ester bond or an amide segment represented by the general formula (4) within the range not impairing the effect of the invention.

-NR ⁶ -C(＝O)- (4)

In the formula, R ⁶ represents an organic group with 1 to 10 carbon atoms or a hydrogen atom.

A cured product obtained from a curable composition containing a polyoxyalkylene-based polymer (A) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonds or the like. However, the polyoxyalkylene-based polymer (A) containing an amide segment or the like may be broken by heat or the like. In addition, a curable composition containing a polyoxyalkylene polymer (A) containing an amide segment or the like tends to have a high viscosity. In view of the above advantages and disadvantages, as the polyoxyalkylene-based polymer (A), polyoxyalkylenes containing amide segments or the like may be used, or polyoxyalkylenes not containing amide segments or the like may be used.

Examples of the amide segment represented by the above general formula (4) include chains formed by, for example, a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate, a reaction between an isocyanate group and an amino group, and a reaction between an isocyanate group and a mercapto group. part. In addition, a segment formed by the reaction of the aforementioned amide segment containing an active hydrogen atom with an isocyanate group is also included in the amide segment represented by the general formula (4).

As a method for producing the polyoxyalkylene-based polymer (A) containing an amide segment, for example, reacting an excess polyisocyanate compound with a polyoxyalkylene compound having an active hydrogen-containing group at the terminal to synthesize a polyoxyalkylene polymer having an isocyanate at the terminal A method of reacting the Z group of the silicon compound represented by the general formula (5) with all or part of the isocyanate groups of the synthesized polymer after or simultaneously with the synthesis.

ZR ⁷ -SiR ⁵ _c X _3-c (5)

(In the formula, R ⁵ , X and c are the same as above. R ⁷ is a divalent organic group, preferably a divalent hydrocarbon group with 1 to 20 carbon atoms. Z is a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group or a secondary amino group. Amino.)

The silicon compound represented by the above general formula (5) is not particularly limited, and examples thereof include: γ-aminopropyldimethoxymethylsilane, γ-aminopropyltrimethoxysilane, N-(β-amino Ethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, (N-phenyl)-γ-aminopropyltrimethoxysilane Amino-containing silanes such as oxysilane and N-ethylaminoisobutyltrimethoxysilane; γ-hydroxypropyltrimethoxysilane and other hydroxy-containing silanes; Triethoxysilane and other mercapto-containing silanes; etc. In addition, such as Japanese Patent Application No. 6-211879 (U.S. Patent No. 5,364,955), Japanese Patent Application No. 10-53637 (U.S. Patent No. 5,756,751), Japanese Patent Application No. 10-204144 (EP0831108), Japanese Patent Application No. 2000-169544, As described in Japanese Patent Application Laid-Open No. 2000-169545, Michael addition reaction products of various α,β-unsaturated carbonyl compounds and primary amino-containing silanes, or various (meth)acryloyl-containing silanes and The Michael addition reaction product of the primary amino compound is used as the silicon compound represented by the above general formula (5).

In addition, examples of a method for producing the amide segment-containing polyoxyalkylene-based polymer (A) include combining a reactive silyl group-containing isocyanate compound represented by the general formula (6) with an active hydrogen-containing group at the terminal. The method of polyoxyalkylene reaction.

O=C=NR ⁷ -SiR ⁵ _c X _3-c (6)

(In the formula, R ⁷ , R ⁵ , X and c are the same as above.)

The reactive silicon group-containing isocyanate compound represented by the above general formula (6) is not particularly limited, and examples thereof include: γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, γ-(methoxymethyl)dimethoxysilylpropyl isocyanate, Trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, ( Methoxymethyl)dimethoxysilylmethyl isocyanate and the like.

When the polyoxyalkylene polymer (A) contains an amide segment, the number (average value) of the amide segment per molecule of the polyoxyalkylene polymer (A) is preferably 1 to 10, more preferably 1.5 ~5, particularly preferably 2~3. When this number is less than 1, curability may be insufficient, and conversely, when it exceeds 10, the polyoxyalkylene-based polymer (A) may become highly viscous and may become difficult to handle. In order to reduce the viscosity of the curable composition and improve handleability, it is preferable that the polyoxyalkylene-based polymer (A) does not contain an amide segment.

＜＜Reactive silicon group-containing (meth)acrylate polymer (B)＞＞

(Meth)acrylates constituting the main chain of the reactive silicon group-containing (meth)acrylate polymer (B) (also referred to as "(meth)acrylate polymer (B)") The monomer is not particularly limited, and various substances can be used. Specific examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate ) isobutyl acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate base) phenyl acrylate, cresyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxy butyl (meth) acrylate, (methoxy) Base) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, (3-trimethoxymethyl)acrylate Silyl)propyl, (3-dimethoxymethylsilyl)propyl (meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate, (meth)acrylic acid (2-dimethoxymethylsilyl)ethyl ester, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ( Ethylene oxide adduct of meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate Ethyl ester, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, perfluoroethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(meth)acrylate (Trifluoromethyl)methyl ester, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-(meth)acrylate (Meth)acrylic monomers such as perfluorodecylethyl ester and 2-perfluorohexadecylethyl (meth)acrylate.

Examples of monomer units other than those mentioned above include acrylic acid such as acrylic acid and methacrylic acid; amide group-containing monomers such as N-methylol methacrylic acid amide and N-methylol methacrylic acid amide; glycidyl acrylate; Epoxy group-containing monomers such as glycidyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and other nitrogen-containing group-containing monomers, etc.

As the (meth)acrylate polymer (B), a polymer obtained by copolymerizing a (meth)acrylate monomer and a vinyl monomer copolymerizable therewith can also be used. The vinyl-based monomer is not particularly limited, and examples thereof include styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, and salts thereof; perfluoroethylene , perfluoropropylene, vinylidene fluoride and other fluorine-containing vinyl monomers; vinyltrimethoxysilane, vinyltriethoxysilane and other silicon-containing vinyl monomers; maleic anhydride, maleic acid, maleic acid Mono- and di-alkyl esters of maleic acid; fumaric acid, mono- and di-alkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide Imine, Propylmaleimide, Butylmaleimide, Hexylmaleimide, Octylmaleimide, Laurylmaleimide, Stearylmaleimide Maleimide monomers such as imine, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; acrylic acid amide, formaldehyde Acrylic acid amide and other amide-containing vinyl monomers; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and other vinyl ester monomers; ethylene, propylene, etc. Vinyl monomers; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. These monomers can also be used as copolymers Element.

Among the (meth)acrylate-based polymers obtained from the above-mentioned monomers, a copolymer formed of a (meth)acrylate-based monomer and a styrene-based monomer optionally added has excellent physical properties, and is therefore preferred. More preferably, it is a (meth)acrylate polymer which consists of an acrylate monomer and a methacrylate monomer, Especially preferably, it is an acrylate polymer which consists of an acrylate monomer.

The (meth)acrylate polymer (B) has a reactive silicon group represented by the general formula (1) shown above. The reactive silicon group contained in the (meth)acrylate polymer (B) may be the same as or different from the reactive silicon group contained in the polyoxyalkylene polymer (A).

Specific examples of ^R5 include methyl, ethyl, chloromethyl, methoxymethyl, and N,N-diethylaminomethyl, preferably methyl and ethyl.

Examples of X include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoxime group, amino group, amido group, acid amido group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, alkoxy groups such as methoxy and ethoxy are more preferable from the viewpoint of mild hydrolyzability and ease of handling, and methoxy and ethoxy are particularly preferable.

Specific examples of the reactive silicon group possessed by the (meth)acrylate polymer (B) include a trimethoxysilyl group, a triethoxysilyl group, and a tris(2-propenyloxy)silyl group. group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxymethylsilyl group Silyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N -Diethylaminomethyl)dimethoxysilyl, (N,N-diethylaminomethyl)diethoxysilyl and the like are not limited thereto. Among them, methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxy Dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group show very high activity and can be obtained with good Cured products with excellent mechanical properties are preferred. From the viewpoint that a cured product having a high Young's modulus can be obtained, a trimethoxysilyl group and a triethoxysilyl group are more preferable, and a trimethoxysilyl group is still more preferable.

The reactive silicon group equivalent of the (meth)acrylate polymer (B) is not particularly limited, but is preferably at least 0.1 mmol/g, more preferably at least 0.5 mmol/g, and still more preferably at least 0.6 mmol/g. The above-mentioned reactive silicon group equivalent is preferably 2.0 mmol/g or less, and more preferably 1.0 mmol/g or less from the viewpoint of suppressing a decrease in the elongation of the cured product. In addition, in order to obtain a highly rigid cured product having a high Young's modulus, it is particularly preferable that the reactive silicon group equivalent is 0.6 mmol/g or more and 1.0 mmol/g or less.

The method for introducing a reactive silicon group into a (meth)acrylate polymer is not particularly limited, and the following methods, for example, can be used.

(iv) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silicon-containing group together with the above monomer. When this method is used, reactive silicon groups tend to be randomly introduced into the main chain of the polymer.

(v) A method of polymerizing into a (meth)acrylate polymer using a mercaptosilane compound having a reactive silicon-containing group as a chain transfer agent. Using this method, reactive silicon groups can be introduced into the polymer ends.

(vi) A method of reacting a compound having a reactive silicon group and a functional group reactive with the V group after copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group (V group). Specific examples include: reacting an isocyanate silane having a reactive silicon-containing group after copolymerizing 2-hydroxyethyl acrylate; reacting an isocyanate silane having a reactive silicon-containing group after copolymerizing glycidyl acrylate; The method of reacting the aminosilane compound of the group, etc.

(vii) A method of modifying terminal functional groups of (meth)acrylate polymers synthesized by living radical polymerization to introduce reactive silicon groups. The (meth)acrylate polymer obtained by the living radical polymerization method is easy to introduce a functional group at the end of the polymer, and by modifying this, it is possible to introduce a reactive silicon group at the end of the polymer.

Examples of the silicon compound that can be used for the reactive silicon group introduced into the (meth)acrylate polymer (B) by the method described above include the following compounds. Examples of the compound having a polymerizable unsaturated group and a reactive silicon-containing group used in the method (iv) include: 3-(dimethoxymethylsilyl)propyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, (dimethoxymethylmethylmethacrylate) Silyl)methyl ester, (trimethoxysilyl)methyl (meth)acrylate, (triethoxysilyl)methyl (meth)acrylate, 3-((methoxy)(meth)acrylate (methyl)dimethoxysilyl)propyl ester, etc. From the viewpoint of availability, 3-(dimethoxymethylsilyl)propyl (meth)acrylate and 3-(trimethoxysilyl)propyl (meth)acrylate are particularly preferable.

As the mercaptosilane compound having a reactive silicon-containing group used in the method (v), 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl base) dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane, etc.

As a compound having a reactive silicon group and a functional group reactive with the V group used in method (vi), 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltrimethoxy Silane, 3-isocyanatopropyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane and other isocyanate silane compounds;3 -Glycidoxypropyldimethoxymethylsilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropyltriethoxysilane, Glycidoxypropyl Methyltrimethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyltriethoxysilane and other epoxysilane compounds; 3-aminopropyldimethoxymethylsilane Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxy Aminosilane compounds such as silane, N-cyclohexylaminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, and the like.

In the method (vii), any modification reaction can be used, for example, a method using a compound having a functional group and a reactive silicon group capable of reacting with a terminal reactive group obtained by polymerization; The compound of the functional group and the double bond which the reactive group reacts introduces a double bond into a polymer terminal, and the method which introduces a reactive silicon group into it by hydrosilylation etc., etc.

It should be noted that these methods can be used in any combination. For example, by combining method (vi) and method (v), a (meth)acrylate polymer (B) having a reactive silicon group at both a molecular chain terminal and/or a side chain can be obtained.

When the (meth)acrylate-based polymer (B) contains a polymer having a (meth)acrylic acid alkyl group having 1 to 3 alkyl carbon atoms in an amount of 40% by weight or more of the total monomers, it becomes highly rigid, Therefore preferred. The (meth)acrylic acid ester polymer (B) may consist only of the above-mentioned polymer containing (meth)acrylic acid alkyl groups having 1 to 3 alkyl carbon atoms in an amount of 40% by weight or more of all monomers, or A polymer containing a (meth)acrylic alkyl group having an alkyl group of 4 to 30 carbon atoms in an amount of at least 40% by weight of all monomers can be included together with the polymer, and the two can be combined to improve rigidity and elongation , strength, and therefore preferred.

In addition, the (meth)acrylate polymer (B) contains 40% by weight or more of a (meth)acrylic acid alkyl group containing 1 to 3 alkyl carbon atoms in all monomers and the number of alkyl carbon atoms is A polymer obtained by copolymerizing a monomer mixture in which the (meth)acrylic acid alkyl group of 4 to 30 is 40% by weight or more in all monomers is preferable because rigidity, elongation, and strength can be improved.

Next, the (meth)acrylate polymer (B) polymerized using the macromonomer which is one of preferable aspects of a (meth)acrylate polymer (B) is demonstrated.

The (meth)acrylate polymer (B) polymerized using a macromonomer is a polymer composed of monomers (b1) and macromonomers (b2), and the monomer (b1 ) has a reactive silicon group and a polymerizable unsaturated group represented by the above-mentioned general formula (1), and the macromonomer (b2) is a (meth)acrylate polymer having a polymerizable unsaturated group thing. The polymer may further have an alkyl (meth)acrylate (b3) having 1 to 3 alkyl carbon atoms as a constituent monomer. In addition, in this application, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid."

(Monomer (b1) having a reactive silicon group and a polymerizable unsaturated group)

Examples of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group include 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxy Propyltriethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, (meth)acryloxymethyltrimethoxysilane, (meth)acryloyl Compounds with (meth)acryloyloxy and reactive silicon groups such as oxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyltriethoxysilane, etc. have vinyl and reactive Silicon-based compounds, etc. These compounds may be used alone or in combination of two or more.

The total content of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group is relative to the total amount of the (meth)acrylate polymer (B) polymerized using the macromonomer (b2). The monomer content is preferably 0.1% by weight to 50% by weight, more preferably 0.5% by weight to 30% by weight, still more preferably 1% by weight to 20% by weight.

(macromonomer (b2))

The macromonomer (b2) is a (meth)acrylate polymer having a polymerizable unsaturated group. Although the macromonomer (b2) itself is a polymer, it can be copolymerized with the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group through the above-mentioned polymerizable unsaturated group, and is a constituent (methyl) ) a monomer of the acrylate polymer (B).

The main chain skeleton of the macromonomer (b2) is a (meth)acrylate polymer. The monomer constituting the main chain skeleton of the macromonomer (b2) is not particularly limited, and various monomers can be used. Examples of (meth)acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylic acid Isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, (meth)acrylate Base) cyclohexyl acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate ester, lauryl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, cresyl (meth)acrylate, benzyl (meth)acrylate, (meth) 2-methoxyethyl acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid Ethylene oxide adduct, 2,2,2-trifluoroethyl (meth)acrylate, 3,3,3-trifluoropropyl (meth)acrylate, 3,3,4 (meth)acrylate ,4,4-pentafluorobutyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, trifluoromethyl (meth)acrylate, perfluoroethyl (meth)acrylate , Bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate , Tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, etc.

In addition, other monomers showing copolymerizability with the above-mentioned (meth)acrylic monomers can also be used. Examples of other monomers include styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid; perfluoroethylene, perfluoropropylene, and vinylidene fluoride; fluorine-containing vinyl monomers; maleic acid, maleic anhydride, maleic acid monoalkyl ester, maleic acid dialkyl ester and other maleic acid and its derivatives; fumaric acid, fumaric acid monoalkyl Fumaric acid and its derivatives such as esters and dialkyl fumarates; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butyl Maleimide, Hexylmaleimide, Octylmaleimide, Dodecylmaleimide, Stearylmaleimide, Phenylmaleimide, Cyclohexyl Maleimide monomers such as maleimide; vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; ethylene, propylene Olefin monomers such as butadiene, isoprene and other conjugated diene monomers; (meth)acrylic acid amide; (meth)acrylonitrile; vinyl chloride, vinylidene chloride, allyl chloride, Vinyl monomers such as allyl alcohol, ethyl vinyl ether, butyl vinyl ether, etc. Other monomers may be used alone or in combination of two or more.

The macromonomer (b2) has a polymerizable unsaturated group and thus exhibits polymerizability. In the macromonomer (b2), the polymerizable unsaturated group may be introduced into either the molecular chain terminal or the side chain of the (meth)acrylate polymer, and is preferably introduced into the end of the molecular chain.

The polymerizable unsaturated group possessed by the macromonomer (b2) is not particularly limited as long as it is a polymerizable unsaturated group in a normal radical polymerization method, for example, an acryloyl group , Methacryl, Vinyl, Allyl, Methallyl, etc. From the viewpoint of exhibiting good polymerizability, acryloyl groups and methacryloyl groups are preferable.

The method for introducing a polymerizable unsaturated group into the macromonomer (b2) is not particularly limited, and methods shown in, for example, the following (viii) to (x) can be used.

(viii) A method of copolymerizing a monomer having two types of polymerizable unsaturated groups having different reactivity (for example, allyl acrylate, etc.) and a monomer having a (meth)acrylic structure.

(ix) After copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group (Z group) (for example, acrylic acid, 2-hydroxyethyl acrylate) and a monomer having a (meth)acrylic structure, the A method of reacting a compound having a polymerizable unsaturated group and a functional group reactive with the Z group (for example, diethyl (meth)acrylate isocyanate, etc.).

(x) A method of introducing a polymerizable unsaturated group into a molecular chain terminal after polymerizing a monomer having a (meth)acrylic structure by a living radical polymerization method.

It should be noted that these methods can be used in any combination.

Among these methods, the method (x) is preferably used because a polymerizable unsaturated group can be introduced into a molecular chain terminal. "Living radical polymerization method" can include, for example: the method using a cobalt porphyrin complex as shown in Journal of American Chemical Society (J.Am.Chem.Soc.), 1994, volume 116, page 7943; Japan The method of using nitroxide free radicals as shown in the special publication No. 2003-500378; the use of organic halides, halogenated sulfonyl compounds, etc. Atom transfer radical polymerization (Atom Transfer Radical Polymerization: ATRP method) in which a metal complex is used as a catalyst, and the like. Since it is easy to introduce a polymerizable unsaturated group at the terminal, the atom transfer radical polymerization method is most preferable.

Alternatively, a method of obtaining a (meth)acrylic polymer using a metallocene catalyst and a thiol compound having at least one reactive silicon group in the molecule as disclosed in JP-A-2001-040037 can also be used.

It is preferable that the polymerizable unsaturated group which a macromonomer (b2) has has a structure represented by the following general formula (7).

CH ₂ =C(R ⁸ )-COO-Z (7)

(In the formula, ^R represents hydrogen or a methyl group. Z represents the main chain skeleton of the macromonomer (b2).)

The number average molecular weight of the macromonomer (b2) is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and preferably 50,000 or less, more preferably 30,000 or less. When the number average molecular weight of a macromonomer (b2) is small, the viscosity of a (meth)acrylate polymer (B) will fall, and there exists a tendency for favorable adhesiveness not to be acquired. On the other hand, when the number average molecular weight of the macromonomer (b2) is too large, the viscosity tends to be too high, which tends to make handling difficult.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the macromonomer (b2) is not particularly limited, but is preferably narrow, more preferably less than 2.0, still more preferably 1.6 or less, particularly preferably 1.5 or less, and more preferably It is particularly preferably 1.4 or less, further particularly preferably 1.3 or less, and most preferably 1.2 or less.

The number average molecular weight (Mn) and weight average molecular weight (Mw) of a macromonomer (b2) are the values measured by GPC (polystyrene conversion), and the detailed measurement method is described in an Example.

The (meth)acrylate polymer (B) is composed of a macromonomer (b2) and other monomers, and the main chain of the (meth)acrylate polymer (B) is called a dry chain, A polymer chain branched from the above-mentioned main chain derived from the macromonomer (b2) is called a branched chain. The monomers constituting the main chain and the branch chains are composed of the above-mentioned monomers and are not particularly limited. From the viewpoint of obtaining good adhesiveness, it is preferable that the Tg of the branched chain is lower than the Tg of the dry chain.

The Tg of the dry chain is preferably -60°C to 150°C, more preferably 0°C to 130°C, still more preferably 30°C to 100°C.

The Tg of the branched chain is preferably -100°C to 150°C, more preferably -90°C to 100°C, even more preferably -80°C to 50°C. Tg was calculated|required by the following Fox formula.

Fox style:

1/(Tg(K))＝Σ(Mi/Tgi)

(In the formula, Mi represents the weight fraction of the monomer i component constituting the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of the monomer i.)

The glass transition temperature of the homopolymer is based on the glass transition temperature (Tg) described in POLYMER HANDBOOK-FOURTH EDITION-(J. Brandrup et al.). When Tg is calculated by Fox's formula, monomers having reactive silicon groups are not included in the calculation.

The total content of the macromonomer (b2) is preferably 1% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, based on all monomers constituting the (meth)acrylate polymer (B). % by weight or less, more preferably 10% by weight or more and 30% by weight or less.

The macromonomer (b2) may be introduced into either the molecular chain terminal or the side chain of the (meth)acrylate polymer (B), but is preferably introduced into the side chain from the viewpoint of adhesiveness. The average number of macromonomers contained in one molecule of the (meth)acrylate polymer (B) is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, and preferably 2.0 or less, more preferably 1.5 or less, more preferably 1.3 or less.

(Alkyl (meth)acrylate (b3))

The alkyl group constituting the alkyl (meth)acrylate (b3) is an alkyl group having 1 to 3 carbon atoms. Specific examples of this (b3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. These may be used alone or in combination of two or more.

From the viewpoint of achieving both flexibility and high rigidity, the (meth)acrylate alkyl The total content of the base ester (b3) is preferably 40% by weight or more, more preferably 45% by weight or more, still more preferably 50% by weight or more, still more preferably 55% by weight or more, and still more preferably 60% by weight or more. In addition, from the viewpoint of durable adhesiveness, it is preferably 50% by weight or more, more preferably 55% by weight or more, and even more preferably More than 60% by weight. In order to ensure compatibility with the polyoxyalkylene polymer (A), it is preferably 70% by weight or less, more preferably 65% by weight or less.

The (meth)acrylic ester polymer (B) polymerized using the macromonomer (b2) is a polymer that uses at least the monomer (b1) and the macromonomer (b2) as constituent monomers, and the The monomer (b1) has a reactive silicon group and a polymerizable unsaturated group, and may contain an alkyl (meth)acrylate with 1 to 3 carbon atoms (b3), other monomers as a constituent unit. Examples of such monomers include (meth)acrylic monomers other than (b1) to (b3) and monomers other than (meth)acrylic monomers. Specifically, for Various monomers exemplified by the above-mentioned macromonomer (b2).

The (meth)acrylate polymer (B) polymerized from the macromonomer (b2) can be obtained by copolymerizing the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group with other monomers And synthetic. Thereby, reactive silicon groups can be randomly introduced into the main chain of the polymer. However, in order to further introduce a reactive silicon group into the (meth)acrylate polymer (B), the above methods may be used in combination.

The monomer composition of the (meth)acrylate polymer (B) can be selected according to the application and purpose, and in applications requiring strength, the glass transition temperature (Tg) is preferably high, preferably 0°C or higher and 200°C Below, it is more preferable to have a Tg of 20° C. or more and 100° C. or less. In addition, Tg was calculated|required by the above-mentioned Fox formula.

The number average molecular weight of the (meth)acrylate polymer (B) is not particularly limited, but is preferably 500 or more and 50,000 or less, more preferably 500 or more and 30,000 or less, in terms of polystyrene-equivalent molecular weight measured by GPC. Preferably, it is 1,000 or more and 10,000 or less. Among them, the number average molecular weight of the (meth)acrylate polymer (B) is preferably 3,000 or less from the viewpoint of exhibiting good adhesiveness even after the heat-and-moisture resistance test.

(Meth)acrylic acid esters have been proposed in Japanese Patent Application Publication No. 59-122541, Japanese Patent Application Publication No. 63-112642, Japanese Patent Application Publication No. 6-172631, Japanese Patent Application Publication No. 11-116763, etc. A method of mixing the polymer (B) and the polyoxyalkylene polymer (A). In addition, a method of polymerizing a (meth)acrylate monomer in the presence of a polyoxypropylene-based polymer having a reactive silicon group can also be utilized.

Preferably, the weight ratio (A):(B) of the polyoxyalkylene polymer (A) to the (meth)acrylate polymer (B) is 95:5 to 50:50, that is, the ratio of (A) is 50 % by weight or more and 95% by weight or less. By being within this range, a cured product showing flexibility and high shear adhesive strength can be obtained. Furthermore, (A):(B) is preferably 80:20 to 50:50, more preferably 70:30 to 50:50, from the viewpoint of achieving both high rigidity and flexibility.

＜＜Epoxy resin (C)＞＞

Examples of the epoxy resin (C) include flame retardant epoxy resins such as epichlorohydrin-bisphenol A epoxy resins, epichlorohydrin-bisphenol F epoxy resins, and glycidyl ether of tetrabromobisphenol A. Oxygen resin, novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-hydroxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol-based epoxy resin, diaminodiphenylmethane-based epoxy resin, carbamate-modified epoxy resin, various alicyclic epoxy resins, N,N-diglycidylaniline, N, Glycidyl ethers of polyols such as N-diglycidyl o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin, and hydantoin-type epoxy resins , petroleum resin, etc., such as epoxy resins of unsaturated polymers, but are not limited thereto, and commonly used epoxy resins can be used. It is preferably an epoxy resin having at least two epoxy groups in 1 molecule from the viewpoints of high reactivity during curing and easy formation of a three-dimensional network in the cured product. As a more preferable epoxy resin, a bisphenol A type epoxy resin, a novolac type epoxy resin, etc. are mentioned.

Preferably, the weight ratio [(A+B):(C)] of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B) to the epoxy resin (C) is 90: The amount of the epoxy resin (C) is 10 to 50:50, that is, the ratio of (A+B) is 50% by weight or more and 90% by weight or less. When the ratio of (A+B) exceeds 90% by weight, the strength decreases, and when it is less than 50% by weight, the flexibility decreases and becomes too hard. Furthermore, from the viewpoint of the balance of flexibility and strength, it is more preferably 80:20 to 60:40.

Young's modulus is an index showing rigidity, and the Young's modulus shown by the cured product obtained by curing the curable composition of this embodiment can be determined by the polyoxyalkylene-based polymer (A) and ( The weight ratio of a meth)acrylate polymer (B) and an epoxy resin (C) can be adjusted arbitrarily. For example, in order to obtain a cured product with a Young's modulus of less than 100 MPa measured at 23°C, it is preferable to set (A):(B) to 95:5 to 60:40, and to set (A+B):(C) to 90:10~60:40.

In addition, in order to obtain a cured product having a Young's modulus measured at 23°C of 100 MPa or more, it is preferable to set (A):(B) to 80:20 to 50:50, and to set (A+B):(C) to 80:20 to 50:50.

＜＜Epoxy resin curing agent with tertiary amine (D)＞＞

As the epoxy resin curing agent (D) for curing the epoxy resin (C), an epoxy resin curing agent having a tertiary amine is preferably used. By using an epoxy resin curing agent (D) having a tertiary amine, a cured product having high rigidity, high strength, and high elongation can be obtained. However, in the first aspect, the epoxy resin curing agent is a compound other than an amine having an alicyclic structure described later. In addition, in the second aspect, the epoxy resin curing agent is a compound other than the amino alcohol compound described later. The tertiary amine in the second aspect may have a phenolic hydroxyl group although it does not have an alcoholic hydroxyl group.

As the epoxy resin curing agent (D) having a tertiary amine, any compound having a tertiary amine can be used. Specifically, for example: N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,6-diaminohexane , N,N-Dimethylbenzylamine, N-methyl-N-(dimethylaminopropyl)aminoethanol, 2,4,6-tris(dimethylaminomethyl)phenol, tripropylamine, DBU , DBN, and salts of these tertiary amines, but not limited thereto. Moreover, you may use 2 or more types together, and you may add a well-known epoxy resin hardening agent other than (D)component further.

The epoxy resin curing agent (D) having a tertiary amine is preferably an aromatic amine, and more preferably has three or more amino groups. Specifically, 2,4,6-tris(dimethylaminomethyl)phenol can be exemplified.

The amount of the epoxy resin curing agent (D) is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 40 parts by weight, and even more preferably 0.5 parts by weight to 100 parts by weight of the epoxy resin (C). More than 30 parts by weight and less than or equal to 30 parts by weight.

＜＜Amine (E1) with alicyclic structure＞＞

The amine (E1) having an alicyclic structure used in the first aspect is an organic compound having an amino group and an alicyclic structure. By blending this compound, the curable composition of the first aspect can express high rigidity through a short heating process.

As an amine (E1) which has an alicyclic structure, the amine which has an alicyclic structure and does not have an aromatic group or a heterocyclic group is preferable. In addition, amines belonging to the above-mentioned epoxy resin curing agent (D) having a tertiary amine are not included as the amine (E1) having an alicyclic structure. Therefore, as the amine (E1) having an alicyclic structure, a primary or secondary amine having an alicyclic structure is preferable. Furthermore, as the amine (E1) having an alicyclic structure, a compound in which an amino group is directly bonded to an alicyclic skeleton is particularly preferable from the viewpoint of a high effect of expressing rigidity by a short-time heating step.

The alicyclic structure of the amine (E1) is not particularly limited, and may be either saturated or unsaturated, and any of monocyclic, bicyclic, and polycyclic. Specific examples of the alicyclic structure include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

Specific examples of the amine (E1) having an alicyclic structure are not particularly limited, and include: isophoronediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis (2-methylcyclohexylamine), cyclohexylamine, dicyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, norbornenediamine, 1,2-diaminocyclohexane, Ancamine2167 , Ancamine 2264 (manufactured by Evonik), etc. In addition, modified products of these can also be used. Specifically, Ancamine 1618, Ancamine 2074, Ancamine 2596, Ancamine 2199, Sunmide IM-544, Sunmide I-544, Ancamine 2075, Ancamine 2280, Ancamine 1934, Ancamine 2228 manufactured by Evonik; 、DAITOCURAR B-1616; LAMIRON C-260 manufactured by BASF Corporation; FujiCure FXD-821 and FujiCure 4233 manufactured by T&K TOKA Corporation; These can be used individually by 1 type or in mixture of 2 or more types.

The amount of the amine (E1) having an alicyclic structure is preferably 1 part by weight to 40 parts by weight, more preferably 3 parts by weight to 35 parts by weight, and even more preferably 100 parts by weight of the epoxy resin (C). It is not less than 5 parts by weight and not more than 25 parts by weight.

＜＜Amino alcohol compound (E2)＞＞

The aminoalcohol compound (E2) used in the second aspect is an organic compound having an amino group and an alcoholic hydroxyl group. By blending this compound, the curable composition of the second aspect can express high rigidity through a short heating process. It should be noted that a hydroxyl group bonded to an aromatic ring is called a phenolic hydroxyl group, and is not included in the alcoholic hydroxyl group described in this application.

The aminoalcohol compound (E2) is preferably an aminoalcohol compound having no aromatic ring, and specifically preferably an aliphatic compound having an amino group and an alcoholic hydroxyl group or an alicyclic compound having an amino group and an alcoholic hydroxyl group. It is more preferably an aliphatic compound having an amino group and an alcoholic hydroxyl group, and still more preferably an alkane compound having an amino group and an alcoholic hydroxyl group. Specific examples include: monoolamines such as methanolamine, ethanolamine, propanolamine, dimethylaminoethanol, and N-methylethanolamine; glycolamines such as diethanolamine and dipropanolamine; triethanolamine and tripranolamine, etc. Triolamine etc. Triolamine is preferred, triethanolamine is particularly preferred.

The amount of the amino alcohol compound (E2) to be used is preferably 1 part by weight to 40 parts by weight, more preferably 3 parts by weight to 35 parts by weight, and still more preferably 5 parts by weight, based on 100 parts by weight of the epoxy resin (C). Above and below 25 parts by weight.

In addition, the amine (E1) which has an alicyclic structure, and an amino alcohol compound (E2) can be used together.

＜＜Silanol Condensation Catalyst (F)＞＞

In order to accelerate the reaction of condensing the reactive silicon groups of the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based polymer (B) to allow chain extension or crosslinking of the polymer, it is preferable to use a silanol condensation catalyst (F).

Examples of the silanol condensation catalyst (F) include organotin compounds, metal carboxylate salts, amine compounds, carboxylic acids, and metal alkoxides.

Specific examples of organotin compounds include: dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin di(butylmaleate), dibutyltin diacetate, dibutyltin oxide, dibutylbis(acetyl Acetonate) tin, dioctyl bis(acetylacetonate) tin, dioctyl tin dilaurate, dioctyl tin distearate, dioctyl tin diacetate, dioctyl tin oxide, dibutyl tin oxide and silicate compounds Products, reaction products of dioctyltin oxide and silicate compounds, reaction products of dibutyltin oxide and phthalates, etc.

Specific examples of carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, and iron carboxylate. As the carboxylate metal salt, the following carboxylic acids can be combined with various metals.

Specific examples of amine compounds include: octylamine, 2-ethylhexylamine, laurylamine, stearylamine and other amines; pyridine, 1,8-diazabicyclo[5,4,0]undecyl -7-ene (DBU), 1,5-diazabicyclo[4,3,0]non-5-ene (DBN) and other nitrogen-containing heterocyclic compounds; guanidine, phenylguanidine, diphenylguanidine, etc. Guanidines; butylbiguanide, 1-o-tolubiguanide, 1-phenylbiguanide and other biguanides; amino-containing silane coupling agents; ketimine compounds, etc.

Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and tertiary carbonic acid.

Specific examples of metal alkoxides include titanium compounds such as tetrabutyl titanate tetra(acetylacetonate)titanium, diisopropoxybis(ethylacetoacetonate)titanium, tris(acetylacetonate)aluminum, diisopropoxy Aluminum compounds such as ethylaluminum propoxyacetoacetate, and zirconium compounds such as zirconium tetrakis(acetylacetonate).

When using the silanol condensation catalyst (F), the amount used is preferably 0.001 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B). It is more than or equal to 20 weight parts, More preferably, it is 0.01 weight part or more and 15 weight parts or less, More preferably, it is 0.01 weight part or more and 10 weight parts or less.

＜＜Water (G)＞＞

Water (G) may be added to B agent of a curable composition. By adding water, curing of the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based polymer (B) can be accelerated when the A agent and the B agent are mixed.

The amount of water (G) added is preferably not less than 0.1 parts by weight and not more than 10 parts by weight, more preferably Preferably it is 0.1 weight part or more and 5 weight parts or less, More preferably, it is 0.1 weight part or more and 2 weight parts or less. In addition, the curable composition may contain agent C containing water (G) in addition to agent A and agent B. In this case, the curable composition is a three-component type.

＜＜Other additives＞＞

In addition to polyoxyalkylene polymer (A), (meth)acrylate polymer (B), epoxy resin (C), epoxy resin curing agent (D), and alicyclic structure in the curable composition In addition to the amine (E1), amino alcohol compound (E2), silanol condensation catalyst (F), water (G), fillers, tackifiers, anti-dripping agents, antioxidants, light stabilizers, UV absorbers, tackifying resins, and other resins are used as additives. In addition, various additives may be added to the curable composition as necessary in order to adjust various physical properties of the curable composition or cured product. Examples of such additives include plasticizers, solvents, diluents, photocurable substances, oxygen-curable substances, surface modifiers, silicates, curing modifiers, and radical inhibitors. , metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, foaming agents, etc.

＜Filler＞

Various fillers can be blended in the curable composition. Examples of fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, Silicon oxide, silicon dioxide, hydrated silica, alumina, carbon black, ferric oxide, aluminum micropowder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament, etc. Since thixotropy can be imparted efficiently, use of fumed silica is more preferable.

The filler is preferably used in an amount of 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, based on a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B). .

Organic hollow spheres and inorganic hollow spheres may be added for the purpose of reducing the weight (lower specific gravity) of the composition.

＜Tackifier＞

A tackifier may be added to the curable composition.

As a tackifier, a silane coupling agent or a reaction product of a silane coupling agent can be added.

Specific examples of silane coupling agents include: γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane Amino-containing silanes such as oxysilane; Methyltrimethoxysilane, α-isocyanatomethyldimethoxymethylsilane and other isocyanate-containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ- Mercapto-containing silanes such as mercaptopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane epoxy silanes.

The said thickener may be used only by 1 type, and may mix and use 2 or more types. In addition, reaction products of various silane coupling agents can also be used.

The amount of the tackifier used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B). share.

＜Anti-dripping agent＞

An anti-dripping agent may be added to the curable composition in order to prevent dripping and improve handleability as necessary. The anti-dripping agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-dripping agents may be used alone or in combination of two or more.

The amount of the anti-dripping agent used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based polymer (B).

＜Antioxidant＞

Antioxidants (antiaging agents) are used in curable compositions. When an antioxidant is used, the weather resistance of the cured product can be improved. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.

The amount of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B) in total. share.

＜Light Stabilizer＞

A photostabilizer may be used in the curable composition. When a light stabilizer is used, it is possible to prevent photooxidative deterioration of the cured product. Examples of light stabilizers include benzotriazoles, hindered amines, and benzoate compounds, among which hindered amines are particularly preferred.

The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B) in total. share.

＜UV absorbers＞

A UV absorber can be used in a curable composition. When using a UV absorber, the surface weather resistance of the cured product can be improved. Examples of ultraviolet absorbers include benzophenones, benzotriazoles, salicylates, substituted cresyls, and metal chelate compounds. Benzotriazoles are particularly preferred. Commercially available names are Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (above, manufactured by BASF Corporation).

The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B) in total. share.

＜Tackifying resin＞

A tackifying resin may be added to the curable composition in order to improve the adhesiveness and adhesiveness to the substrate, or according to other needs. The tackifying resin is not particularly limited, and commonly used tackifying resins can be used.

As specific examples, terpene-based resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene- Phenolic resins, coumarone-indene resins, rosin resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and Hydrides, petroleum resins (for example, C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, etc. These may be used individually or in combination of 2 or more types.

The amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B). parts, more preferably 5 to 30 parts by weight.

＜＜Preparation of Curable Composition＞＞

For the curable composition of the first aspect, it is preferable to mix a polyoxyalkylene polymer (A), an acrylate polymer (B), an epoxy resin curing agent (D), an amine having an alicyclic structure ( E1) and other additives are used as A agent, and epoxy resin (C) and other additives are used as B agent to make a two-component type in which A agent and B agent are mixed before use. In addition, in order to accelerate the curing reaction of the polyoxyalkylene polymer (A) and the acrylate polymer (B), a silanol condensation catalyst (F) and/or water (G) may be added to the B agent.

For the curable composition of the second aspect, it is preferable to mix a polyoxyalkylene polymer (A), an acrylate polymer (B), an epoxy resin curing agent (D), and other additives as the A agent, and the ring Oxygen resin (C) and other additives are used as agent B, and it is made into a two-component type in which agent A and agent B are mixed before use. The amino alcohol compound (E2) may be blended with either or both of the A agent and the B agent. In addition, in order to accelerate the curing reaction of the polyoxyalkylene polymer (A) and the acrylate polymer (B), a silanol condensation catalyst (F) and/or water (G) may be added to the B agent.

The curable composition of the present embodiment may be cured at room temperature or may be cured by heating. In the case of bonding dissimilar materials with an adhesive, especially when heat curing is performed, thermal deformation due to differences in linear expansion coefficients of the dissimilar materials may become a problem. Generally, when reaction-curable adhesives such as epoxy-based compositions and highly rigid urethane-based compositions are heated and cured, while obtaining high adhesive strength, flexibility is greatly reduced, and heat may sometimes be generated during cooling. out of shape. On the other hand, the curable composition according to the present embodiment is rubbery with a Young's modulus of several MPa to several tens of MPa even if it is heated and cured to the extent that high adhesive strength can be obtained, and thermal deformation can be suppressed. In addition, since high rigidity can be exhibited by subsequent curing at room temperature, it is possible to manufacture a highly rigid adhesive that does not undergo thermal deformation.

The Young's modulus at 23° C. of the cured product obtained by curing the curable composition of the present embodiment is preferably 90 MPa or more, more preferably 200 MPa or more, from the viewpoint of achieving both high rigidity and flexibility. In addition, the elongation at break at 23° C. is preferably 70% or more, more preferably 80% or more. The measuring methods of Young's modulus and elongation at break follow the methods described in the Examples.

＜＜Surface treatment of adherend＞＞

The curable composition of the present embodiment can exhibit good adhesiveness to various adherends such as plastics, metals, and composite materials. In addition, when used as an adhesive to nonpolar materials such as polypropylene and engineering plastics having rigid molecular chains such as polyphenylene sulfide, in order to improve the adhesiveness to these adherends, obtain To ensure stable adhesive strength, the surface of the adherend can be treated in advance by known methods. For example, surface treatment techniques such as grinding treatment, flame treatment, corona discharge, arc discharge, plasma treatment, etc. can be used. From the viewpoint of less damage to the adherend and stable adhesiveness, plasma treatment is preferable. These surface treatments are also effective for removing the release agent remaining on the surface of the adherend used during molding.

The curable composition according to the present embodiment has the characteristics of expressing target physical properties by performing a long-term curing (curing) step after joining the adherend, and having a rapid increase in rigidity. That is, when the semi-cured product is obtained by applying a short heating process to the curable composition before curing after bonding of the adherend, although the semi-cured product does not reach the final target rigidity, it can exhibit A certain degree of rigidity. Therefore, the curable composition according to the present embodiment can be suitably used as a structural adhesive for joining adherends in a continuous line production system.

The conditions of the aforementioned short-time heating step are not particularly limited, and examples thereof include a temperature of 50 to 200° C., a time of 1 minute to 1 hour, and the like.

In addition, the conditions of the final curing (curing) step for making the curable composition exhibit the final target physical properties performed after the short-time heating step are not particularly limited, and for example, a temperature of 5 to 50° C. , 24 hours to 1 week as the time, etc.

＜＜Application＞＞

The curable composition is suitable for use as an adhesive composition, and can be used for sealing materials, adhesives, adhesives, waterproofing materials, etc. of structures, ships, automobiles, roads, and the like. The cured product obtained by curing the curable composition has not only high rigidity but also flexibility, and is more preferably used as an adhesive, especially a structural adhesive, in the above applications. In particular, when joining dissimilar materials such as aluminum-steel and aluminum-composite materials, thermal deformation occurs due to temperature changes due to the difference in linear expansion coefficient between the two. In such a case, in order to cope with thermal deformation, an adhesive having a high elongation is preferable, so the curable composition can be suitably used for joining the above-mentioned dissimilar materials. In the joining of dissimilar materials, it is preferable to coat the joining portion with a sealant in order to prevent corrosion. As sealants, polymers with reactive silicon groups as shown in this application can be used. As an application using the curable composition, it is preferably used in automobile parts such as vehicle panels, large vehicle parts such as trucks and buses, parts for train vehicles, parts for airplanes, parts for ships, motor parts, various machine parts, etc. used for adhesives.

Example

Hereinafter, although an Example is given and this invention is demonstrated concretely, this Example does not limit this invention.

The number average molecular weights in Examples are GPC molecular weights measured under the following conditions.

Liquid delivery system: HLC-8120GPC manufactured by Tosoh Corporation

Chromatographic column: TSK-GEL H type manufactured by Tosoh Corporation

Solvent: THF

Molecular weight: converted to polystyrene

Measuring temperature: 40°C

The terminal group-equivalent molecular weight in the examples is based on the hydroxyl value obtained by the measurement method of JIS K 1557, the iodine value obtained by the measurement method of JIS K 0070, and the structure of the organic polymer (the composition determined by the polymerization initiator used). Dendrome) and calculated molecular weight.

The average number of introduced carbon-carbon unsaturated bonds per terminal of the polymer (Q) shown in the examples was calculated by the following calculation formula.

(Average amount introduced) = [unsaturated group concentration of polymer (Q) obtained from iodine value (mol/g) - unsaturated group concentration of precursor polymer (P) obtained from iodine value ( mol/g)]/[the hydroxyl group concentration (mol/g) of the precursor polymer (P) obtained from the hydroxyl value].

The average number of introduced silyl groups per terminal of the polymer (A) shown in the Examples was calculated by NMR measurement.

(Synthesis Example 1)

Polyoxypropylene glycol with a number average molecular weight of about 2,000 is used as an initiator to polymerize propylene oxide under a zinc hexacyanocobaltate ethylene glycol dimethyl ether complex catalyst to obtain a number average molecular weight with hydroxyl groups at both ends Polyoxypropylene (P-1) having a molecular weight of 28,500 (molecular weight in terms of terminal groups: 17,700) and molecular weight distribution Mw/Mn=1.21. 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After methanol was distilled off by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130° C. for 2 hours. Then, methanol solution of 0.28 molar equivalent of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was further added to convert terminal hydroxyl group into allyl group. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, after removing water by centrifugation, further mixing and stirring water in the obtained hexane solution 300 parts by weight, after removing water by centrifugation again, hexane was removed by vacuum devolatilization. Thus, polyoxypropylene (Q-1) having a terminal structure having two or more carbon-carbon unsaturated bonds was obtained. It is known that polymer (Q-1) has an average of 2.0 carbon-carbon unsaturated bonds introduced into one terminal site.

With respect to 100 parts by weight of the obtained polyoxypropylene (Q-1) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site, a divinyldisiloxane platinum complex (calculated as platinum in terms of 3% by weight of isopropanol solution) 36 ppm, while stirring, 2.2 parts by weight of trimethoxysilane was slowly added dropwise. After reacting the mixed solution at 90° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain an The linear reactive silicon group-containing polyoxypropylene polymer (A-1) has an average of 3.2 silicon groups and a number average molecular weight of 28,500.

(Synthesis Example 2)

48.6 parts by weight of isobutanol was added to a four-necked flask equipped with a stirrer, and the temperature was raised to 105° C. under a nitrogen atmosphere. Spending 5 hours therein, the following mixed solution was added dropwise. The mixed solution was 65.0 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 3-methacryloxypropyltrimethoxy 10.0 parts by weight of silane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) were dissolved in 22.7 parts by weight of isobutanol. Furthermore, polymerization was carried out at 105°C for 2 hours to obtain a reactive silicon group-containing (meth)acrylate polymer (B-1) having an average of 1.6 silicon groups per molecule and a number average molecular weight of 2,300. isobutanol solution (solid content 60%). The reactive silicon group equivalent of the solid content was 0.72 mmol/g.

(Synthesis Example 3)

0.42 weight part of cuprous bromide and 20.0 weight part of butyl acrylates were added to the reactor in a deoxidized state, and it heated and stirred. 8.8 parts by weight of acetonitrile as a polymerization solvent and 1.90 parts by weight of ethyl 2-bromoadipate as an initiator were added and mixed, and pentamethyldiethylenetriamine ( Hereinafter abbreviated as triamine), initiates the polymerization reaction. Next, 80.0 parts by weight of butyl acrylate was gradually added to perform a polymerization reaction. During the polymerization process, add triamine appropriately to adjust the polymerization speed. The total amount of triamines used in the polymerization was 0.15 parts by weight. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, vacuum devolatilization was performed to remove volatile components and obtain a polymer concentrate.

Dilute the above-mentioned concentrate with toluene, add filter aid, adsorbent (KYOWAAD 700SEN: manufactured by Kyowa Chemical Co., Ltd.), hydrotalcite (KYOWAAD 500SH: manufactured by Kyowa Chemical Co., Ltd.), heat to about 80-100°C and stir, The solid content was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a crude purified polymer.

Add the crude purified polymer, 1.98 parts by weight of potassium acrylate, 100 ppm of 4-hydroxyl-TEMPO, and 100 parts by weight of dimethylacetamide as a solvent, and react at 70°C for 3 hours, then distill off the solvent under reduced pressure to obtain polymer concentrate. The concentrate was diluted with toluene, and the solid content was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a macromonomer (b2-1) having a number average molecular weight of 10,500 (GPC molecular weight) and a molecular weight distribution (Mw/Mn) of 1.18 having an acryloyl group at one terminal.

(Synthesis Example 4)

48.0 parts by weight of isobutanol was added to a four-necked flask equipped with a stirrer, and the temperature was raised to 105°C in a nitrogen atmosphere. Spending 5 hours therein, the following mixed solution was added dropwise. The mixed solution was 60.0 parts by weight of methyl methacrylate, 10.0 parts by weight of stearyl methacrylate, and the macromonomer (b2- 1) 20 parts by weight, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2,2'-azobis(2-methyl 2.5 parts by weight of butyronitrile) dissolved in 22.7 parts by weight of isobutanol. Further, polymerization was carried out at 105° C. for 2 hours to obtain an isobutanol solution (solid ingredients 60%). The macromonomer equivalent of the solid content of this solution was 0.018 mmol/g, and the reactive silicon group equivalent was 0.72 mmol/g.

(Example 1)

42 parts by weight of the polyoxypropylene polymer (A-1) containing reactive silicon groups obtained in Synthesis Example 1 and the (meth)acrylic acid ester polymer (B-1) obtained in Synthesis Example 2 in solid content After mixing so as to form 28 parts by weight, isobutanol was heated and devolatilized. 4 parts by weight of Ancamine K54 (manufactured by 2,4,6-tris(dimethylaminomethyl)phenol Evonik Co., Ltd.) as an epoxy resin curing agent (D) and an amine having an alicyclic structure were mixed into the obtained mixture. (E1) isophorone diamine (another name: 3-(aminomethyl)-3,5,5-trimethylcyclohexylamine) 3 parts by weight, KBM-603 (N- (2-aminoethyl)-3-aminopropyltrimethoxysilane Shin-Etsu Chemical Co., Ltd.) 2 parts by weight, and the obtained mixture was made A agent. 30 parts by weight of jER828 (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation) as the epoxy resin (C), NEOSTANN U-810 (dioctyltin dilaurate Nitto Kasei) as the silanol condensation catalyst (F) Co., Ltd.) 0.3 parts by weight and 0.5 parts by weight of water were mixed as agent B.

(dumbbell tensile properties)

Agent A and agent B were mixed to form a sheet having a thickness of about 2 mm, and a heating process was performed at 80° C. for 30 minutes. The sheet was punched into a No. 3 dumbbell shape, and the tensile strength test was carried out at 23°C and 50% RH, and the stress at 30% elongation (M30), the strength at break (TB), and the elongation at break (EB) were measured. , and Young's modulus. Tensile physical properties other than Young's modulus were measured at a tensile speed of 200 mm/min using AutoGraph (AGS-J) manufactured by Shimadzu Corporation. The Young's modulus was measured in the range of 0.05 to 0.3% displacement at a tensile speed of 10 mm/min. The results are shown in Table 1.

(Example 2-3 and Comparative Example 1-4)

Except having changed to the compounding shown in Table 1, the composition was produced similarly to Example 1, and the evaluation of the tensile physical property of a dumbbell was performed. The results are shown in Table 1.

In addition, the following compounds were used in Table 1.

(1): 2,4,6-tris(dimethylaminomethyl)phenol (Evonik)

(2): 4,4'-Diaminodicyclohexylmethane

(3): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

(4): bisphenol A epoxy resin (Mitsubishi Chemical Corporation)

(5): Dioctyltin dilaurate (Nitto Kasei Co., Ltd.)

As shown in Table 1, compared with Comparative Example 1 in which the amine (E1) having the alicyclic structure was not incorporated, in Examples 1-3 in which the amine (E1) having the alicyclic structure was blended, the temperature passed through 80°C The short heating step of 30 minutes showed high rigidity (Young's modulus), and it was found that the rigidity shown by the heating step was improved by blending the amine (E1) having an alicyclic structure.

In addition, compared with Example 3 using an amine compound in which an amino group is not directly bonded to an alicyclic skeleton, Examples 1 and 2 using an amine compound in which an amino group is directly bonded to an alicyclic skeleton are obtained by the above-mentioned The rigidity exhibited by the heating process is high.

On the other hand, Comparative Example 2-4 in which an amine compound not having an alicyclic structure was blended showed the same rigidity as that of Comparative Example 1. From this, it can be seen that the improvement effect of rigidity is peculiar to the amine (E1) which has an alicyclic structure.

In addition, in Example 1, A agent and B agent were mixed as described above to make a sheet with a thickness of about 2 mm, and after a heating process at 80° C. for 30 minutes, further curing was carried out at 23° C. for 7 days, and then , the sheet was punched into a No. 3 dumbbell shape as described above, and a tensile strength test was carried out. The measured M30 was 10.5 MPa, TB was 14.0 MPa, Young's modulus was 270 MPa, and EB was 230%. Thus, the curable composition of Example 1 exhibited good physical properties of a cured product that can be used as a structural adhesive after curing for a sufficient time.

(Example 4)

The polyoxypropylene polymer (A-1) 42 weight parts that contain reactive silicon group that obtains in the synthesis example 1 and the (meth)acrylic acid ester polymer (B-2) that obtains in the synthesis example 4 take solid content as 28 parts by weight were mixed, and the isobutanol was heated and devolatilized. 7 parts by weight of Ancamine K54 (manufactured by 2,4,6-tris(dimethylaminomethyl)phenol Evonik Co., Ltd.) as an epoxy resin curing agent (D) and an amine having an alicyclic structure were mixed with the obtained mixture. (E1) 4 parts by weight of Amicure PACM (4,4'-diaminodicyclohexylmethane manufactured by Evonik), 7 parts by weight of p-dodecylphenol as a phenolic compound, and KBM-603 as a silane coupling agent (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight, AEROSIL R-202 (hydrophobic fumed silica manufactured by NIPPONAEROSIL Corporation) as a filler ) and 4.5 parts by weight of AEROSIL 300 (manufactured by NIPPON AEROSIL Co., Ltd., hydrophilic fumed silica), and the resulting mixture was used as agent A.

31.7 parts by weight of jER828 (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation) as the epoxy resin (C), 4 parts by weight of SYLOPHOBIC 200 (hydrophobic colloidal silica, FUJI SILYSIA CHEMICAL Co., Ltd.) as the filler, and 1.5 parts by weight of AEROSIL R-202 (manufactured by NIPPON AEROSIL Co., Ltd., hydrophobic fumed silica), and 0.3 parts by weight of NEOSTANN U-810 (manufactured by Nitto Kasei Co., Ltd.) as a silanol condensation catalyst (F). part, 0.5 parts by weight of water mixed as the B agent.

In the same manner as in Example 1, dumbbell tensile physical properties were evaluated. However, the curing conditions were changed to conditions of curing for 7 days at 23° C. and a relative humidity of 50% after heating at 80° C. for 15 minutes. The results are shown in Table 2.

(Example 5)

Except having changed to the compounding shown in Table 2, the composition was produced similarly to Example 4, and the evaluation of the tensile physical property of a dumbbell was performed. The results are shown in Table 2.

In addition, the following compounds were used in Table 2.

(1): 2,4,6-tris(dimethylaminomethyl)phenol (Evonik)

(2): 4,4'-Diaminodicyclohexylmethane

(3): 3,3'-Dimethyl-4,4'-diaminodicyclohexylmethane

(4): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

(5): Hydrophobic fumed silica (NIPPON AEROSIL)

(6): Hydrophilic fumed silica (NIPPON AEROSIL)

(7): bisphenol A epoxy resin (Mitsubishi Chemical Corporation)

(8): Hydrophobic colloidal silica (FUJI SILYSIA CHEMICAL)

(9): Dioctyltin dilaurate (Nitto Kasei Co., Ltd.)

[Table 2]

As shown in Table 2, it can be seen that in Examples 4 and 5, as the amine (E1) having an alicyclic structure, a compound in which an amino group is directly bonded to an alicyclic skeleton is used, and a sufficient period of maintenance is carried out to obtain Cured product with high rigidity (Young's modulus).

(Example 6)

42 parts by weight of the polyoxypropylene polymer (A-1) containing reactive silicon groups obtained in Synthesis Example 1 and the (meth)acrylic acid ester polymer (B-1) obtained in Synthesis Example 2 in solid content After mixing so as to form 28 parts by weight, isobutanol was heated and devolatilized. 4 parts by weight of Ancamine K54 (manufactured by 2,4,6-tris(dimethylaminomethyl)phenol Evonik) as an epoxy resin curing agent (D) and 4 parts by weight of an amino alcohol compound (E2) were mixed into the obtained mixture. 3 parts by weight of triethanolamine, 2 parts by weight of KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a silane coupling agent, the resulting mixture As an A agent. 30 parts by weight of jER828 (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation) as the epoxy resin (C), NEOSTANN U-810 (dioctyltin dilaurate Nitto Kasei) as the silanol condensation catalyst (F) Co., Ltd.) 0.3 parts by weight and 0.5 parts by weight of water were mixed as agent B.

In the same manner as in Example 1, dumbbell tensile physical properties were evaluated. The results are shown in Table 3.

(Example 7 and Comparative Examples 5-6)

A composition was prepared in the same manner as in Example 6 except that the formulations shown in Table 3 were changed, and dumbbell tensile physical properties were evaluated. The results are shown in Table 3.

In addition, the following compounds were used in Table 3.

(1): 2,4,6-tris(dimethylaminomethyl)phenol (Evonik)

(2): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

(3): Bisphenol A epoxy resin (Mitsubishi Chemical Corporation)

(4): Dioctyltin dilaurate (Nitto Kasei Co., Ltd.)

[table 3]

As shown in Table 3, compared with Comparative Example 5 in which the aminoalcohol compound (E2) was not compounded or Comparative Example 6 in which the epoxy resin (C) was not compounded, in Example 6 and the compounded aminoalcohol compound (E2) In 7, the rigidity (Young's modulus) exhibited by a short-time heating step at 80° C. for 30 minutes was high. In addition, it was found that Example 6 in which triethanolamine was blended as a triolamine had higher rigidity than Example 7 in which 2-dimethylaminoethanol was blended as a monoolamine.

In addition, for Example 6, the A agent and the B agent were mixed as described above to form a sheet with a thickness of about 2mm, and after a heating process at 80°C for 30 minutes, it was further cured at 23°C for 7 days, and then, as described above The sheet was punched into a No. 3 dumbbell shape, and the tensile strength test was carried out. The measured M30 is 6.0MPa, TB is 9.2MPa, Young's modulus is 90MPa, and EB is 180%. Thus, the curable composition of Example 6 exhibited good physical properties of a cured product that can be used as a structural adhesive after curing for a sufficient period of time.

Claims (19)

1. A multi-component curable composition comprising A agent and B agent, The A agent includes a polyoxyalkylene polymer (A) having a reactive silicon group represented by the general formula (1), a (meth)acrylate having a reactive silicon group represented by the general formula (1) A polymer (B), an epoxy resin curing agent (D) having a tertiary amine other than an amine having an alicyclic structure, and an amine (E1) having an alicyclic structure, Described B agent comprises epoxy resin (C), -SiR ⁵ _c X _3-c (1) In formula (1), R ⁵ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and c represents 0 or 1. 2. The multi-component curable composition according to claim 1, wherein: The amine (E1) having an alicyclic structure is a compound in which an amino group is directly bonded to an alicyclic skeleton. 3. The multi-component curable composition according to claim 1 or 2, wherein: The reactive silicon group of the polyoxyalkylene polymer (A) is a trimethoxysilyl group. 4. The multi-component curable composition according to claim 1 or 2, wherein: The reactive silicon group of the (meth)acrylate polymer (B) is a trimethoxysilyl group. 5. The multi-component curable composition according to claim 1 or 2, wherein: The terminal portion of the polyoxyalkylene polymer (A) is represented by the general formula (2),

In formula (2), R ¹ and R ³ are each independently a divalent bonding group having 1 to 6 carbon atoms, and atoms bonded to each carbon atom adjacent to R ¹ and R ³ are carbon, Any atom in oxygen and nitrogen, R ² and R ⁴ are each independently hydrogen or a hydrocarbon group with 1 to 10 carbon atoms, n is an integer of 1 to 10, and R ⁵ is a substituted or unsubstituted carbon atom with 1 to 10 carbon atoms. 20 is a hydrocarbon group, X is a hydroxyl group or a hydrolyzable group, and c represents 0 or 1. 6. The multi-component curable composition according to claim 5, wherein, R ¹ is CH ₂ OCH ₂ , and R ³ is CH ₂ . 7. The multi-component curable composition according to claim 5, wherein, R ² and R ⁴ are hydrogen atoms, respectively. 8. The multi-component curable composition according to claim 1 or 2, wherein: (Meth)acrylic ester polymer (B) is a polymer composed of monomer (b1) and macromonomer (b2), and the monomer (b1) has a reactive silicon group and a polymerizable An unsaturated group, the macromonomer (b2) is a (meth)acrylate polymer having a polymerizable unsaturated group. 9. A multi-component curable composition comprising agent A and agent B, The A agent includes a polyoxyalkylene polymer (A) having a reactive silicon group represented by the general formula (1), a (meth)acrylate having a reactive silicon group represented by the general formula (1) polymer (B), and an epoxy resin curing agent (D) having a tertiary amine other than an aminoalcohol compound, Described B agent comprises epoxy resin (C), Either or both of agent A and agent B contain an aminoalcohol compound (E2), -SiR ⁵ _c X _3-c (1) In formula (1), R ⁵ is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and c represents 0 or 1. 10. The multi-component curable composition according to claim 9, wherein: The aminoalcohol compound (E2) is an aminoalcohol compound not having an aromatic ring. 11. The multi-component curable composition according to claim 9 or 10, wherein, The aminoalcohol compound (E2) is a triolamine. 12. The multi-component curable composition according to claim 9 or 10, wherein, The reactive silicon group of the polyoxyalkylene polymer (A) is a trimethoxysilyl group. 13. The multi-component curable composition according to claim 9 or 10, wherein, The reactive silicon group of the (meth)acrylate polymer (B) is a trimethoxysilyl group. 14. The multi-component curable composition according to claim 9 or 10, wherein, The terminal portion of the polyoxyalkylene polymer (A) is represented by the general formula (2),

In formula (2), R ¹ and R ³ are each independently a divalent bonding group having 1 to 6 carbon atoms, and atoms bonded to each carbon atom adjacent to R ¹ and R ³ are carbon, Any atom in oxygen and nitrogen, R ² and R ⁴ are each independently hydrogen or a hydrocarbon group with 1 to 10 carbon atoms, n is an integer of 1 to 10, and R ⁵ is a substituted or unsubstituted carbon atom with 1 to 10 carbon atoms. 20 is a hydrocarbon group, X is a hydroxyl group or a hydrolyzable group, and c represents 0 or 1. 15. The multi-component curable composition according to claim 14, wherein, R ¹ is CH ₂ OCH ₂ , and R ³ is CH ₂ . 16. The multi-component curable composition according to claim 14, wherein, R ² and R ⁴ are hydrogen atoms, respectively. 17. The multi-component curable composition according to claim 9 or 10, wherein, (Meth)acrylic ester polymer (B) is a polymer composed of monomer (b1) and macromonomer (b2), and the monomer (b1) has a reactive silicon group and a polymerizable An unsaturated group, the macromonomer (b2) is a (meth)acrylate polymer having a polymerizable unsaturated group. 18. A structural adhesive comprising the multi-component curable composition according to any one of claims 1 to 17. 19. A cured product obtained by curing the multi-component curable composition according to any one of claims 1 to 17.